CN112608486A - High-conductivity carbon nanotube grafted polyurethane composite material and preparation method thereof - Google Patents

High-conductivity carbon nanotube grafted polyurethane composite material and preparation method thereof Download PDF

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CN112608486A
CN112608486A CN202011391756.5A CN202011391756A CN112608486A CN 112608486 A CN112608486 A CN 112608486A CN 202011391756 A CN202011391756 A CN 202011391756A CN 112608486 A CN112608486 A CN 112608486A
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polyurethane
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吴敏
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Tongxiang Jingxiang New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention relates to the technical field of polyurethane materials, and discloses a high-conductivity carbon nano tube grafted polyurethane composite material, wherein an acyl chloride group and hydroxyl of propargyl alcohol are subjected to esterification reaction to obtain an alkynyl carbon nano tube, 2, 2-bis (azidomethyl) propane-1, 3-diol is used as a diol micromolecule chain extender, the diol micromolecule chain extender participates in the polyurethane polymerization process to obtain polyurethane containing an azido group, the azido group of the polyurethane and the alkynyl of the carbon nano tube are subjected to high-efficiency click reaction to obtain the carbon nano tube grafted polyurethane composite material, a chemical bond covalent grafting method improves the interface interaction and compatibility of the carbon nano tube and the polyurethane, reduces the agglomeration phenomenon of the carbon nano tube, the highly dispersed carbon nano tube forms a three-dimensional conductive network in the polyurethane, enhances the conductivity and the electric conductivity of the material, and the carbon nano tube with excellent mechanical property is used as a crosslinking center, the tensile strength of the polyurethane is obviously improved.

Description

High-conductivity carbon nanotube grafted polyurethane composite material and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a high-conductivity carbon nanotube grafted polyurethane composite material and a preparation method thereof.
Background
The polyurethane is classified into polyester type and polyether type, can be processed into coatings, elastomers, fibers and the like, has the advantages of no toxicity, good film-forming property, excellent elasticity and good heat and sound insulation effect, is widely applied to the aspects of building industry, automobile manufacturing industry, aviation industry, medical industry and the like, so the development of production and life is met through the comprehensive performance of the polyurethane, but the traditional polyurethane material has higher intrinsic resistivity and poorer electric conductivity, the development of the polyurethane material is limited, usually, a conductive agent can be added to be physically blended with the polyurethane, such as conductive carbon black, graphite fibers, metal conductive particles and the like, but the addition amount of the conductive agent is large, and the physical blending method can greatly influence the mechanical properties of the polyurethane material, such as tensile strength and the like.
The carbon nano tube has a one-dimensional nano structure, has unique mechanical, thermal and electrical properties, is an ideal reinforcing filler for preparing organic-inorganic composite materials, has wide research and application in epoxy resin, polyurethane and acrylic resin, but is poor in compatibility and interface interaction with polyurethane due to the structural characteristics and chemical inertness of the surface of the carbon nano tube, is difficult to uniformly disperse in a polyurethane material matrix, is easy to form agglomeration, causes poor reinforcing effect of the carbon nano tube, and is difficult to obtain a polyurethane composite material with excellent performance, so that the interface modification of the carbon nano tube is carried out, and the improvement of the dispersibility of the carbon nano tube in polyurethane by covalent grafting, non-covalent modification and other methods becomes a research hotspot and difficulty.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-conductivity carbon nanotube grafted polyurethane composite material and a preparation method thereof, and solves the problems of poor compatibility and interface interaction between the carbon nanotube as a conductive agent and polyurethane.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a high-conductivity carbon nanotube grafted polyurethane composite material is as follows:
(1) adding SOCl into conical flask2And heating the carboxylated carbon nano tube in an oil bath reactor to perform an acyl chlorination reaction, and performing reduced pressure distillation, washing with distilled water and acetone for purification to obtain the acyl chlorinated carbon nano tube.
(2) Adding an N, N-dimethylformamide solvent, an acylchlorinated carbon nanotube, propargyl alcohol and a catalyst pyridine into a conical flask, heating in an oil bath reactor until esterification reaction is carried out, carrying out reduced pressure distillation, and washing and purifying with acetone to obtain the alkynyl carbon nanotube.
(3) Adding dimethyl sulfoxide solvent, 2-bis (bromomethyl) -1, 3-propylene glycol and sodium azide into a conical flask, heating in an oil bath reactor for azide reaction, adding distilled water and ethyl acetate for extraction, taking an ethyl acetate organic phase, carrying out reduced pressure distillation and recrystallization purification to obtain the 2, 2-bis (azidomethyl) propane-1, 3-diol with the molecular formula of C5H10N6O2。
(4) Adding polypropylene glycol, isophorone diisocyanate and a catalyst dibutyltin dilaurate into a conical flask in a nitrogen atmosphere, heating to 75-85 ℃ in an oil bath reactor, reacting for 1-2h, adding 2, 2-bis (azidomethyl) propane-1, 3-diol and 1, 4-butanediol serving as micromolecular chain extenders, reacting for 30-60min, and separating and purifying to obtain the azido polyurethane.
(5) Adding N, N-dimethylformamide solvent, polyurethane azide and alkynyl carbon nano tube into a conical flask in nitrogen atmosphere, uniformly dispersing, adding catalyst and cocatalyst, reacting at room temperature for 12-24h, separating and purifying, dissolving the product in acetone solvent, pouring into a mold, defoaming in vacuum, and curing to form a film to obtain the highly conductive carbon nano tube grafted polyurethane composite material.
Preferably, the oil bath reactor in the step (1) comprises an oil bath pan, a heater is arranged below the oil bath pan, a screw rod is fixedly connected inside the oil bath pan, the screw rod is movably connected with an adjusting gear, the adjusting gear is fixedly connected with a base, and a conical flask is arranged above the base.
Preferably, the mass ratio of the carbon oxychloride nanotubes, the propargyl alcohol and the catalyst pyridine in the step (2) is 10:150-250: 8-12.
Preferably, the mass ratio of the polypropylene glycol, the isophorone diisocyanate, the dibutyltin dilaurate, the 2, 2-bis (azidomethyl) propane-1, 3-diol and the 1, 4-butanediol in the step (4) is 100:45-55:0.5-1:2-8: 5-15.
Preferably, the catalyst in the step (5) is cuprous bromide, and the cocatalyst is diethylenetriamine.
Preferably, the mass ratio of the polyurethane azide, the alkynyl carbon nanotube, the cuprous bromide and the diethylenetriamine in the step (5) is 100:2-6:0.2-0.5: 0.35-0.7.
Drawings
FIG. 1 is a structural formula of 2, 2-bis (azidomethyl) propane-1, 3-diol;
FIG. 2 is a schematic view of the oil bath reactor configuration;
FIG. 3 is a schematic view of the base being raised and lowered;
fig. 4 is a partially enlarged schematic view of the adjustment gear.
1-oil bath pan; 2-heating the instrument; 3-a screw; 4-adjusting the gear; 5-a base; 6-conical flask.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
according to the high-conductivity carbon nanotube grafted polyurethane composite material, a carboxylated carbon nanotube is subjected to acyl chlorination, an acyl chloride group is subjected to esterification reaction with hydroxyl of propargyl alcohol to obtain an alkynyl carbon nanotube, an alkynyl functional group is introduced to the surface of the carbon nanotube, 2-bis (azidomethyl) propane-1, 3-diol is used as a diol small molecule chain extender and participates in a polyurethane polymerization process to obtain polyurethane containing an azido group, and the azido group of the polyurethane and the alkynyl of the carbon nanotube are subjected to efficient click reaction under the concerted catalysis of cuprous bromide and diethylenetriamine to obtain the carbon nanotube grafted polyurethane composite material through a chemical grafting method.
Compared with simple physical mixing, the high-conductivity carbon nanotube grafted polyurethane composite material has the advantages that the interface interaction and compatibility of the carbon nanotube and polyurethane are greatly improved by a chemical bond covalent grafting method, the agglomeration phenomenon of the carbon nanotube is remarkably reduced, the highly dispersed carbon nanotube forms a three-dimensional conductive network in the polyurethane, the conductivity and the conductivity of the material are enhanced, and meanwhile, the carbon nanotube with excellent mechanical properties is used as a crosslinking center, so that the mechanical properties such as tensile strength and the like of the polyurethane are obviously improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a high-conductivity carbon nanotube grafted polyurethane composite material is as follows:
(1) adding SOCl into conical flask2And the carboxylation carbon nanotube, in the oil bath reactor, the oil bath reactor includes the oil bath pot, and oil bath pot below is provided with the heating appearance, the inside fixedly connected with screw rod of oil bath pot, screw rod swing joint have adjusting gear, adjusting gear fixedly connected with base, and the base top is provided with the erlenmeyer flask, and the heating carries out the acyl chlorination reaction, and reduced pressure distillation, distilled water and acetone washing purification obtain acyl chlorination carbon nanotube.
(2) Adding N, N-dimethylformamide solvent, acylchlorinated carbon nano-tubes with the mass ratio of 10:150-250:8-12, propargyl alcohol and catalyst pyridine into a conical flask, heating in an oil bath reactor until esterification reaction is carried out, carrying out reduced pressure distillation, washing with acetone and purifying to obtain the alkynyl carbon nano-tubes.
(3) Adding dimethyl sulfoxide solvent, 2-bis (bromomethyl) -1, 3-propylene glycol and sodium azide into a conical flask, heating in an oil bath reactor for azide reaction, adding distilled water and ethyl acetate for extraction, taking an ethyl acetate organic phase, carrying out reduced pressure distillation and recrystallization purification to obtain the 2, 2-bis (azidomethyl) propane-1, 3-diol with the molecular formula of C5H10N6O2。
(4) Adding polypropylene glycol, isophorone diisocyanate and a catalyst dibutyltin dilaurate into a conical flask in a nitrogen atmosphere, heating to 75-85 ℃ in an oil bath reactor, reacting for 1-2h, adding 2, 2-bis (azidomethyl) propane-1, 3-diol and 1, 4-butanediol as small molecular chain extenders, wherein the mass ratio of the polypropylene glycol, the isophorone diisocyanate, the dibutyltin dilaurate, the 2, 2-bis (azidomethyl) propane-1, 3-diol and the 1, 4-butanediol is 100:45-55:0.5-1:2-8:5-15, reacting for 30-60min, and separating and purifying to obtain the azido polyurethane.
(5) Adding N, N-dimethylformamide solvent, polyurethane azide and alkynyl carbon nano tube into a conical flask in nitrogen atmosphere, uniformly dispersing, adding cuprous bromide catalyst and diethylenetriamine cocatalyst into the conical flask, reacting at room temperature for 12-24h, separating and purifying, dissolving the product in acetone solvent, pouring the acetone solvent into a mold, defoaming in vacuum, and curing to form a film to obtain the high-conductivity carbon nano tube grafted polyurethane composite material.
Example 1
(1) Adding SOCl into conical flask2And the carboxylation carbon nanotube, in the oil bath reactor, the oil bath reactor includes the oil bath pot, and oil bath pot below is provided with the heating appearance, the inside fixedly connected with screw rod of oil bath pot, screw rod swing joint have adjusting gear, adjusting gear fixedly connected with base, and the base top is provided with the erlenmeyer flask, and the heating carries out the acyl chlorination reaction, and reduced pressure distillation, distilled water and acetone washing purification obtain acyl chlorination carbon nanotube.
(2) Adding N, N-dimethylformamide solvent, acylchlorinated carbon nano-tubes with the mass ratio of 10:150:8, propargyl alcohol and catalyst pyridine into a conical flask, heating in an oil bath reactor until esterification reaction is carried out, carrying out reduced pressure distillation, washing with acetone and purifying to obtain the alkynyl carbon nano-tubes.
(3) Adding dimethyl sulfoxide solvent, 2-bis (bromomethyl) -1, 3-propylene glycol and sodium azide into a conical flask, heating in an oil bath reactor for azide reaction, adding distilled water and ethyl acetate for extraction, taking an ethyl acetate organic phase, carrying out reduced pressure distillation and recrystallization purification to obtain the 2, 2-bis (azidomethyl) propane-1, 3-diol with the molecular formula of C5H10N6O2。
(4) Adding polypropylene glycol, isophorone diisocyanate and a catalyst dibutyltin dilaurate into a conical flask in a nitrogen atmosphere, heating to 75 ℃ in an oil bath reactor, reacting for 1h, adding 2, 2-bis (azidomethyl) propane-1, 3-diol and 1, 4-butanediol serving as small molecular chain extenders, reacting for 30min, wherein the mass ratio of the polypropylene glycol, the isophorone diisocyanate, the dibutyltin dilaurate to the 2, 2-bis (azidomethyl) propane-1, 3-diol to the 1, 4-butanediol is 100:45:0.5:2:5, and separating and purifying to obtain the azido polyurethane.
(5) Adding N, N-dimethylformamide solvent, polyurethane azide and alkynyl carbon nano tubes into a conical flask in a nitrogen atmosphere, uniformly dispersing, adding cuprous bromide serving as a catalyst and diethylenetriamine serving as a cocatalyst, reacting at room temperature for 12 hours at the mass ratio of 100:2:0.2:0.35, separating and purifying, dissolving the product in acetone solvent, pouring the acetone solvent into a mold, defoaming in vacuum, and curing to form a film to obtain the high-conductivity carbon nano tube grafted polyurethane composite material 1.
Example 2
(1) Adding SOCl into conical flask2And the carboxylation carbon nanotube, in the oil bath reactor, the oil bath reactor includes the oil bath pot, and oil bath pot below is provided with the heating appearance, the inside fixedly connected with screw rod of oil bath pot, screw rod swing joint have adjusting gear, adjusting gear fixedly connected with base, and the base top is provided with the erlenmeyer flask, and the heating carries out the acyl chlorination reaction, and reduced pressure distillation, distilled water and acetone washing purification obtain acyl chlorination carbon nanotube.
(2) Adding N, N-dimethylformamide solvent, acylchlorinated carbon nano-tubes with the mass ratio of 10:180:9, propargyl alcohol and catalyst pyridine into a conical flask, heating in an oil bath reactor until esterification reaction is carried out, carrying out reduced pressure distillation, washing with acetone and purifying to obtain the alkynyl carbon nano-tubes.
(3) Adding dimethyl sulfoxide solvent, 2-bis (bromomethyl) -1, 3-propylene glycol and sodium azide into a conical flask, heating in an oil bath reactor for azide reaction, adding distilled water and ethyl acetate for extraction, taking an ethyl acetate organic phase, carrying out reduced pressure distillation and recrystallization purification to obtain the 2, 2-bis (azidomethyl) propane-1, 3-diol with the molecular formula of C5H10N6O2。
(4) Adding polypropylene glycol, isophorone diisocyanate and a catalyst dibutyltin dilaurate into a conical flask in a nitrogen atmosphere, heating to 80 ℃ in an oil bath reactor, reacting for 1.5h, adding 2, 2-bis (azidomethyl) propane-1, 3-diol and 1, 4-butanediol serving as micromolecule chain extenders, reacting for 60min, wherein the mass ratio of the polypropylene glycol, the isophorone diisocyanate, the dibutyltin dilaurate to the 2, 2-bis (azidomethyl) propane-1, 3-diol to the 1, 4-butanediol is 100:48:0.6:4:8, and separating and purifying to obtain the azido polyurethane.
(5) Adding N, N-dimethylformamide solvent, polyurethane azide and alkynyl carbon nano tubes into a conical flask in a nitrogen atmosphere, uniformly dispersing, adding cuprous bromide serving as a catalyst and diethylenetriamine serving as a cocatalyst, reacting at room temperature for 24 hours according to the mass ratio of 100:3:0.3:0.45, separating and purifying, dissolving the product in acetone solvent, pouring the acetone solvent into a mold, carrying out vacuum defoaming, and curing to form a film, thus obtaining the high-conductivity carbon nano tube grafted polyurethane composite material 2.
Example 3
(1) Adding SOCl into conical flask2And the carboxylation carbon nanotube, in the oil bath reactor, the oil bath reactor includes the oil bath pot, and oil bath pot below is provided with the heating appearance, the inside fixedly connected with screw rod of oil bath pot, screw rod swing joint have adjusting gear, adjusting gear fixedly connected with base, and the base top is provided with the erlenmeyer flask, and the heating carries out the acyl chlorination reaction, and reduced pressure distillation, distilled water and acetone washing purification obtain acyl chlorination carbon nanotube.
(2) Adding N, N-dimethylformamide solvent, acylchlorinated carbon nano-tubes with the mass ratio of 10:220:10.5, propargyl alcohol and catalyst pyridine into a conical flask, heating in an oil bath reactor until esterification reaction is carried out, carrying out reduced pressure distillation, washing with acetone and purifying to obtain the alkynyl carbon nano-tubes.
(3) Adding dimethyl sulfoxide solvent, 2-bis (bromomethyl) -1, 3-propylene glycol and sodium azide into a conical flask, heating in an oil bath reactor for azide reaction, adding distilled water and ethyl acetate for extraction, taking an ethyl acetate organic phase, carrying out reduced pressure distillation and recrystallization purification to obtain the 2, 2-bis (azidomethyl) propane-1, 3-diol with the molecular formula of C5H10N6O2。
(4) Adding polypropylene glycol, isophorone diisocyanate and a catalyst dibutyltin dilaurate into a conical flask in a nitrogen atmosphere, heating to 80 ℃ in an oil bath reactor, reacting for 1.5h, adding 2, 2-bis (azidomethyl) propane-1, 3-diol and 1, 4-butanediol serving as micromolecule chain extenders, reacting for 45min, and separating and purifying to obtain the azido polyurethane, wherein the mass ratio of the polypropylene glycol, the isophorone diisocyanate, the dibutyltin dilaurate to the 2, 2-bis (azidomethyl) propane-1, 3-diol to the 1, 4-butanediol is 100:52:0.85:6: 12.
(5) Adding N, N-dimethylformamide solvent, polyurethane azide and alkynyl carbon nano tubes into a conical flask in a nitrogen atmosphere, uniformly dispersing, adding cuprous bromide serving as a catalyst and diethylenetriamine serving as a cocatalyst, reacting at room temperature for 18 hours according to the mass ratio of 100:4.5:0.4:0.6, separating and purifying, dissolving the product in acetone solvent, pouring the acetone solvent into a mold, defoaming in vacuum, and curing to form a film to obtain the high-conductivity carbon nano tube grafted polyurethane composite material 3.
Example 4
(1) Adding SOCl into conical flask2And the carboxylation carbon nanotube, in the oil bath reactor, the oil bath reactor includes the oil bath pot, and oil bath pot below is provided with the heating appearance, the inside fixedly connected with screw rod of oil bath pot, screw rod swing joint have adjusting gear, adjusting gear fixedly connected with base, and the base top is provided with the erlenmeyer flask, and the heating carries out the acyl chlorination reaction, and reduced pressure distillation, distilled water and acetone washing purification obtain acyl chlorination carbon nanotube.
(2) Adding N, N-dimethylformamide solvent, acylchlorinated carbon nano-tubes with the mass ratio of 10:250:12, propargyl alcohol and catalyst pyridine into a conical flask, heating in an oil bath reactor until esterification reaction is carried out, carrying out reduced pressure distillation, washing with acetone and purifying to obtain the alkynyl carbon nano-tubes.
(3) Adding dimethyl sulfoxide solvent, 2-bis (bromomethyl) -1, 3-propylene glycol and sodium azide into a conical flask, heating in an oil bath reactor for azide reaction, adding distilled water and ethyl acetate for extraction, taking an ethyl acetate organic phase, carrying out reduced pressure distillation and recrystallization purification to obtain the 2, 2-bis (azidomethyl) propane-1, 3-diol with the molecular formula of C5H10N6O2。
(4) Adding polypropylene glycol, isophorone diisocyanate and a catalyst dibutyltin dilaurate into a conical flask in a nitrogen atmosphere, heating to 85 ℃ in an oil bath reactor, reacting for 2h, adding 2, 2-bis (azidomethyl) propane-1, 3-diol and 1, 4-butanediol as small molecular chain extenders, reacting for 60min, and separating and purifying to obtain the azido polyurethane, wherein the mass ratio of the polypropylene glycol, the isophorone diisocyanate, the dibutyltin dilaurate to the 2, 2-bis (azidomethyl) propane-1, 3-diol to the 1, 4-butanediol is 100:55:1:6: 15.
(5) Adding N, N-dimethylformamide solvent, polyurethane azide and alkynyl carbon nano tubes into a conical flask in a nitrogen atmosphere, uniformly dispersing, adding cuprous bromide serving as a catalyst and diethylenetriamine serving as a cocatalyst, reacting at room temperature for 24 hours at the mass ratio of 100:6:0.5:0.7, separating and purifying, dissolving the product in acetone solvent, pouring the acetone solvent into a mold, carrying out vacuum defoaming, and curing to form a film, thus obtaining the high-conductivity carbon nano tube grafted polyurethane composite material 4.
Comparative example 1
(1) Adding SOCl into conical flask2And the carboxylation carbon nanotube, in the oil bath reactor, the oil bath reactor includes the oil bath pot, and oil bath pot below is provided with the heating appearance, the inside fixedly connected with screw rod of oil bath pot, screw rod swing joint have adjusting gear, adjusting gear fixedly connected with base, and the base top is provided with the erlenmeyer flask, and the heating carries out the acyl chlorination reaction, and reduced pressure distillation, distilled water and acetone washing purification obtain acyl chlorination carbon nanotube.
(2) Adding N, N-dimethylformamide solvent, acylchlorinated carbon nano-tubes with the mass ratio of 10:120:6.5, propargyl alcohol and catalyst pyridine into a conical flask, heating in an oil bath reactor until esterification reaction is carried out, carrying out reduced pressure distillation, washing with acetone and purifying to obtain the alkynyl carbon nano-tubes.
(3) Adding dimethyl sulfoxide solvent, 2-bis (bromomethyl) -1, 3-propylene glycol and sodium azide into a conical flask, heating in an oil bath reactor for azide reaction, adding distilled water and ethyl acetate for extraction, taking an ethyl acetate organic phase, carrying out reduced pressure distillation, recrystallizing and purifying to obtain 2, 2-bis (azidomethyl) propane-1, 3-diol, and carrying out molecular purificationFormula is C5H10N6O2。
(4) Adding polypropylene glycol, isophorone diisocyanate and a catalyst dibutyltin dilaurate into a conical flask in a nitrogen atmosphere, heating to 85 ℃ in an oil bath reactor, reacting for 2h, adding 2, 2-bis (azidomethyl) propane-1, 3-diol and 1, 4-butanediol serving as micromolecule chain extenders, reacting for 30min, wherein the mass ratio of the polypropylene glycol, the isophorone diisocyanate, the dibutyltin dilaurate to the 2, 2-bis (azidomethyl) propane-1, 3-diol to the 1, 4-butanediol is 100:40:0.3:0.5:2, and separating and purifying to obtain the azido polyurethane.
(5) Adding N, N-dimethylformamide solvent, polyurethane azide and alkynyl carbon nano tubes into a conical flask in a nitrogen atmosphere, uniformly dispersing, adding cuprous bromide serving as a catalyst and diethylenetriamine serving as a cocatalyst, reacting at room temperature for 24 hours at the mass ratio of 100:1:0.15:0.25, separating and purifying, dissolving the product in acetone solvent, pouring the acetone solvent into a mold, carrying out vacuum defoaming, and curing to form a film, thus obtaining the high-conductivity carbon nano tube grafted polyurethane composite material 1.
In the examples and the comparative examples, the conductivity of the high-conductivity carbon nanotube grafted polyurethane composite material was tested by using an SIN-TDS210 online conductivity meter, and the test standard is GB/T1550-.
Figure BDA0002811145700000101
In the examples and comparative examples, the tensile strength of the highly conductive carbon nanotube-grafted polyurethane composite was tested using an HZ-1009A Universal Material testing machine, test Standard GB/T1040.3-2006.
Figure BDA0002811145700000102

Claims (6)

1. A high-conductivity carbon nanotube grafted polyurethane composite material is characterized in that: the preparation method of the high-conductivity carbon nanotube grafted polyurethane composite material is as follows:
(1) adding SOCl into conical flask2And heating the carboxylated carbon nano tube in an oil bath reactor to perform acyl chlorination reaction to obtain the acyl chlorinated carbon nano tube.
(2) Adding an acylchlorinated carbon nanotube, propargyl alcohol and a catalyst pyridine into an N, N-dimethylformamide solvent, and heating until an esterification reaction is carried out to obtain an alkynylated carbon nanotube.
(3) Adding 2, 2-bis (bromomethyl) -1, 3-propylene glycol and sodium azide into a dimethyl sulfoxide solvent, heating for an azide reaction to obtain 2, 2-bis (azidomethyl) propane-1, 3-diol with a molecular formula of C5H10N6O2。
(4) Adding isophorone diisocyanate and a catalyst dibutyltin dilaurate into polypropylene glycol in a nitrogen atmosphere, heating to 75-85 ℃, reacting for 1-2h, adding 2, 2-bis (azidomethyl) propane-1, 3-diol and 1, 4-butanediol serving as micromolecular chain extenders, and reacting for 30-60min to obtain the azido polyurethane.
(5) In a nitrogen atmosphere, adding polyurethane azide and alkynyl carbon nano tubes into an N, N-dimethylformamide solvent, uniformly dispersing, adding a catalyst and a cocatalyst, reacting at room temperature for 12-24h, dissolving the product in an acetone solvent, pouring the acetone solvent into a mold, performing vacuum defoamation, and curing to form a film to obtain the highly conductive carbon nano tube grafted polyurethane composite material.
2. The highly conductive carbon nanotube-grafted polyurethane composite according to claim 1, wherein: the oil bath reactor in the step (1) comprises an oil bath pot, a heating instrument is arranged below the oil bath pot, a screw rod is fixedly connected inside the oil bath pot, an adjusting gear is movably connected with the screw rod, a base is fixedly connected with the adjusting gear, and a conical flask is arranged above the base.
3. The highly conductive carbon nanotube-grafted polyurethane composite according to claim 1, wherein: the mass ratio of the carbon acyl chloride nanotubes, the propargyl alcohol and the catalyst pyridine in the step (2) is 10:150-250: 8-12.
4. The highly conductive carbon nanotube-grafted polyurethane composite according to claim 1, wherein: the mass ratio of the polypropylene glycol, the isophorone diisocyanate, the dibutyltin dilaurate, the 2, 2-bis (azidomethyl) propane-1, 3-diol and the 1, 4-butanediol in the step (4) is 100:45-55:0.5-1:2-8: 5-15.
5. The highly conductive carbon nanotube-grafted polyurethane composite according to claim 1, wherein: and (3) the catalyst in the step (5) is cuprous bromide, and the cocatalyst is diethylenetriamine.
6. The highly conductive carbon nanotube-grafted polyurethane composite according to claim 1, wherein: the mass ratio of the polyurethane azide, the alkynyl carbon nano tube, the cuprous bromide and the diethylenetriamine in the step (5) is 100:2-6:0.2-0.5: 0.35-0.7.
CN202011391756.5A 2020-12-02 2020-12-02 High-conductivity carbon nanotube grafted polyurethane composite material and preparation method thereof Withdrawn CN112608486A (en)

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CN113668234A (en) * 2021-08-10 2021-11-19 瑞安市博安防刺穿材料科技有限公司 Synthesis method and application of carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber
JP2022165397A (en) * 2021-04-19 2022-10-31 コリア リサーチ インスティテュート オブ ケミカル テクノロジー High-density and high-stability cnt film coated substrate using click reaction and manufacturing method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022165397A (en) * 2021-04-19 2022-10-31 コリア リサーチ インスティテュート オブ ケミカル テクノロジー High-density and high-stability cnt film coated substrate using click reaction and manufacturing method thereof
JP7247399B2 (en) 2021-04-19 2023-03-28 コリア リサーチ インスティテュート オブ ケミカル テクノロジー High density and high stability CNT film coating substrate using click reaction and its manufacturing method
CN113668234A (en) * 2021-08-10 2021-11-19 瑞安市博安防刺穿材料科技有限公司 Synthesis method and application of carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber
CN113668234B (en) * 2021-08-10 2023-02-10 瑞安市博安防刺穿材料科技有限公司 Synthesis method and application of carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber

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